In this work, a modelling research on the separation of ammonia gas from liquid streams via vacuum membrane distillation (VMD) is conducted. An experimentally validated multi-component simulation model of a flat sheet VMD module is developed by implementing heat and mass balances through the feed, membrane and permeate channels. Continuous removal of the gases transferred through the membrane at a constant pressure in the permeate channel is assumed. The transport mechanisms through the pores under VMD conditions for both volatiles are discussed. Under studied VMD conditions and the typical concentration range in waste waters (i.e. 1-10 g TAN l-1), it is observed that none of the two volatile components (ammonia and water) is preferentially transported. The resulting VMD performance is simulated and evaluated in terms of total transmembrane flux, ammonia flux, ammonia selectivity and thermal energy consumption. The model was validated experimentally and showed good agreement, with an average relative error <10%. The experiments were performed with a solution of (NH4)2SO4 in a laboratory set up under controlled conditions. The simulation, as well as the experimental results, emphasize the existing trade-off between the flux (JNH3) and selectivity (SNH3) of ammonia. Increasing feed temperature and decreasing vacuum pressure results in higher JNH3 but lower SNH3. Moreover, those parameters that enhance the heat transfer through the membrane (i.e. feed temperature, pore size, porosity, vacuum pressure, etc.) promote the water flux over ammonia. While those parameters that enhance mixing and the ammonia mass transfer in the feed (i.e. feed velocity, spacer geometry, pH, ammonia feed concentration, etc.) promote the ammonia flux over water. The only operating parameter which enhances simultaneously the JNH3 and SNH3 is the feed velocity, indicating that the spacer geometry can play an important role in designing VMD modules for ammonia separation. VMD can extract and concentrate ammonia on the permeate side at a low specific thermal energy consumption. However, the JNH3 is greatly limited by the feed ammonia concentration which will ultimately determine the cost-effectiveness of the recovery. The trends described by the model are in agreement with other authors’ observations and give insight into the mechanisms dominating ammonia separation via VMD and its performance limits.